Malononitrile compounds and their use as pesticides

ABSTRACT

The present invention relates to malononitrile compounds of formula (Y):  
                 
 
     wherein R 1  and R 2  are the same or different and independently C 1 -C 5  (halo)alkyl, C 2 -C 5  (halo)alkyloxy, C 2 -C 5  (halo)alkenyl, C 2 -C 5  (halo)alkynyl, hydrogen, or cyano; R 3  is C 3 -C 6  (halo)cycloalkyl; m is an integer of 1 to 3; R 5  is halogen, cyano, nitro, C 1 -C 4  (halo)alkyl, or the like; n is an integer of 0 to 4, with the proviso that when n is 2 or more, then R 5 &#39;s are the same or different from each other; R 6  is halogen, cyano, nitro, C 1 -C 4  (halo)alkyl, or the like; as well as pesticide compositions containing these compounds as active ingredients. The present invention makes it possible to effectively control pests such as insect pests, acarine pests, and nematode pests.

TECHNICAL FIELD

[0001] The present invention relates to novel malononitrile compoundsand their use as pesticide compositions.

BACKGROUND ART

[0002] Against pests such as insect pests, acarine pests, and nematodepests, various pesticide compositions have been used so far for theircontrol. The conditions of pesticide compositions required havedrastically been changed, including the care of their effects on theenvironment and the acquisition of drug resistance by pests to becontrolled. Under such circumstances, there have been great demands forthe development of new pesticide compositions.

DISCLOSURE OF INVENTION

[0003] The present inventors have extensively studied to find compoundshaving excellent pest controlling activity. As a result, they have foundthat the malononitrile compounds of formula (Y) as depicted below haveexcellent controlling activity against pests such as insect pests,acarine pests, and nematode pests, thereby reaching the presentinvention.

[0004] That is, the present invention provides malononitrile compoundsof formula (Y):

[0005] (hereinafter referred to as the present compound(s)) wherein R¹and R² are the same or different and independently C₁-C₅ (halo)-alkyl,C₁-C₅ (halo)alkyloxy, C₂-C₅ (halo)alkenyl, C₂-C₅ (halo)alkynyl,hydrogen, or cyano;

[0006] R³ is C₃-C₆ (halo)cycloalkyl;

[0007] m is an integer of 1 to 3;

[0008] R⁵ is halogen, cyano, nitro, C₁-C₄ (halo)alkyl, C₂-C₄(halo)alkenyl, C₂-C₄ (halo)alkynyl, C₁-C₄ (halo)alkyloxy, C₁-C₄(halo)alkylthio, C₁-C₄ (halo)alkylsulfinyl, C₁-C₄ (halo)alkylsulfonyl,C₁-C₄ (halo)alkylcarbonyl, C₁-C₄ (halo)alkyloxycarbonyl, C₁-C₄(halo)alkylcarbonyloxy, phenyloxy, or phenylthio, in which the phenyloxyand phenylthio groups may optionally be substituted with halogen orC₁-C₃ alkyl;

[0009] n is an integer of 0 to 4;

[0010] R⁶ is hydrogen, halogen, cyano, nitro, C₁-C₄ (halo)alkyl, C₂-C₄(halo)alkenyl, C₂-C₄ (halo)alkynyl, C₁-C₄ (halo)alkyloxy, C₁-C₄(halo)alkylthio, C₁-C₄ (halo)alkylsulfinyl, C₁-C₄ (halo)alkylsulfonyl,C₁-C₄ (halo)alkylcarbonyl, C₁-C₄ (halo)alkyloxycarbonyl, C₁-C₄(halo)alkylcarbonyloxy, phenyloxy, or phenylthio, in which the phenyloxyand phenylthio groups may optionally be substituted with halogen orC₁-C₃ alkyl;

[0011] with the proviso that when n is 2 or more, then R⁵'s are the sameor different from each other.

[0012] The present invention also provides pesticide compositionscomprising the present compounds as active ingredients.

MODE FOR CARRYING OUT THE INVENTION

[0013] In the definition of substituents as used herein, each group hasthe following meaning:

[0014] The (halo)alkyl group refers to alkyl optionally substituted withhalogen for one or more than one hydrogen atoms.

[0015] The (halo)alkyloxy group refers to alkyloxy optionallysubstituted with halogen for one or more than one hydrogen atoms.

[0016] The (halo)alkenyl group refers to alkenyl optionally substitutedwith halogen for one or more than one hydrogen atoms.

[0017] The (halo)alkynyl group refers to alkynyl optionally substitutedwith halogen for one or more than one hydrogen atoms.

[0018] The (halo)alkylthio group refers to alkylthio optionallysubstituted with halogen for one or more than one hydrogen atoms.

[0019] The (halo)alkylsulfinyl group refers to alkylsulfinyl optionallysubstituted with halogen for one or more than one hydrogen atoms.

[0020] The (halo)alkylsulfonyl group refers to alkylsulfonyl optionally,substituted with halogen for one or more than one hydrogen atoms.

[0021] The (halo)alkylcarbonyl group refers to alkylcarbonyl optionallysubstituted with halogen for one or more than one hydrogen atoms.

[0022] The (halo)alkyloxycarbonyl group refers to alkyloxycarbonyloptionally substituted with halogen for one or more than one hydrogenatoms.

[0023] The (halo)alkylcarbonyloxy group refers to alkylcarbonyloxyoptionally substituted with halogen for one or more than one hydrogenatoms.

[0024] The (halo)cycloalkyl group refers to cycloalkyl optionallysubstituted with halogen for one or more than one hydrogen atoms.

[0025] The term “C1-C10” or the like refers to number of carbon atomsconstituting the alkyl, alkenyl, or alkynyl group in each substituent.For example, C₁-C₄ (halo)alkylcarbonyl means alkylcarbonyl optionallywith halogen for one or more hydrogen atoms wherein the alkyl part isconstituted by C₁-C₄ carbon atom.

[0026] In the present compounds, each group includes specific ones aslisted below:

[0027] The C₁-C₅ (halo)alkyl group represented by R¹ or R² may includemethyl, ethyl, propyl, 1-methylethyl, 1,1-dimethylethyl,2,2-dimethylpropyl, chloromethyl, fluoromethyl, difluoromethyl,trifluoromethyl, 2,2,2-trifluoroethyl, and 1,1,2,2-tetrafluoroethyl.

[0028] The C₁-C₅ (halo)alkyloxy group represented by R¹ or R² mayinclude methoxy, ethoxy, 1-methylethoxy, trifluoromethoxy,difluoromethoxy, 2,2,2-trifluoroethoxy, and 1,1,2,2-tetrafluoroethoxy.

[0029] The C₂-C₅ (halo)alkenyl group represented by R¹ or R² may includevinyl, 1-propenyl, 2-propenyl, 2,2-difluorovinyl, and1,2,2-trifluorovinyl.

[0030] The C₂-C₅ (halo)alkynyl group represented by R¹ or R² may includeethynyl, 1-propynyl, 2-propynyl and 3,3,3-trifluoro-1-propynyl.

[0031] The C₃-C₆ (halo)cycloalkyl represented by R³ may includecyclopropyl, 2,2-dichloro-1-cyclopropyl, 2,2-difluoro-1-cyclopropyl,2,2,3,3-tetrafluoro-1-cyclopropyl, 2,2-dichloro-1-cyclobutyl,2,2-difluoro-1-cyclobutyl, 2,2,3,3-tetrafluoro-1-cyclobutyl, cyclobutyl,cyclopentyl, and cyclohexyl.

[0032] The halogen atom represented by R⁵ or R⁶ may include fluorine,chlorine, bromine and iodine.

[0033] The C₁-C₄ (halo)alkyl group represented by R⁵ or R⁶ may includemethyl, ethyl, propyl, 1-methylethyl, 1,1-dimethylethyl,trifluoromethyl, pentafluoroethyl, 3,3,3-trifluoroethyl, and1,1,2,2-tetrafluoroethyl.

[0034] The C₂-C₄ (halo)alkenyl group represented by R⁵ or R⁶ may includevinyl, 1-propenyl, 2-propenyl and 2,2-difluorovinyl.

[0035] The C₂-C₄ (halo)alkynyl group represented by R⁵ or R⁶ may includeethynyl, 1-propynyl, 2-propynyl and 3,3,3-trifluoro-1-propynyl.

[0036] The C₁-C₄ (halo)alkyloxy group represented by R⁵ or R⁶ mayinclude methoxy, ethoxy, trifluoromethoxy, bromodifluoromethoxy,difluoromethoxy, chlorodifluoromethoxy, pentafluoroethoxy,2,2,2-trifluoroethoxy, and 1,1,2,2-tetrafluoroethoxy.

[0037] The C₁-C₄ (halo)alkylthio group represented by R⁵ or R⁶ mayinclude methylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, and1,1,2,2-tetrafluoroethylthio.

[0038] The C₁-C₄ (halo)alkylsulfinyl group represented by R⁵ or R⁶ mayinclude methylsulfinyl and trifluoromethylsulfinyl.

[0039] The C₁-C₄ (halo)alkylsulfonyl group represented by R⁵ or R⁶ mayinclude methylsulfonyl and trifluoromethylsulfonyl.

[0040] The C₁-C₄ (halo)alkylcarbonyl group represented by R⁵ or R⁶ mayinclude acetyl and trifluoroacetyl.

[0041] The C₁-C₄ (halo)alkyloxycarbonyl group represented by R⁵ or R⁶may include methoxycarbonyl and 2,2,2-trifluoroethoxycarbonyl.

[0042] The C₁-C₄ (halo)alkylcarbonyloxy group represented by R⁵ or R⁶may include acetyloxy, propionyloxy, and trifluoroacetyloxy.

[0043] The phenyloxy optionally substituted with halogen or C₁-C₃ alkyl,which is represented by R⁵ or R⁶, may include phenoxy, p-methylphenoxy,m-methylphenoxy, and p-chlorophenoxy.

[0044] The phenylthio group optionally substituted with halogen or C₁-C₃alkyl, which is represented by R⁵ or R⁶, may include phenylthio,p-methylphenylthio, m-methylphenylthio, and p-chlorophenylthio.

[0045] The embodiments of the present invention may include thefollowing compounds:

[0046] The malononitrile compounds of formula (Y) wherein R¹ ishydrogen, and R² is C₁-C₅ (halo)alkyl, C₂-C₅ (halo)alkenyl, or hydrogen;

[0047] The malononitrile compounds of formula (Y) wherein R¹ and R² areboth hydrogen;

[0048] The malononitrile compounds of formula (Y) wherein R¹ and R² arethe same or different and independently C₁-C₃ (halo)alkyl, C₁-C₃(halo)alkyloxy, C₂-C₄ (halo)alkenyl, C₂-C₄ (halo)alkynyl, hydrogen, orcyano; R⁵ and R⁶ are the same or different and independently halogen,cyano, nitro, C₁-C₃ haloalkyl, C₁-C₃ haloalkyloxy, C₁-C₃ (halo)akylthio,C₁-C₃ (halo)alkylsulfinyl, C₁-C₃ (halo)alkylsulfonyl, C₁-C₃(halo)alkylcarbonyl, or C₁-C₃ haloalkyloxycarbonyl;

[0049] The malononitrile compounds of formula (Y)-wherein R³ is C₃-C₄(halo)cycloalkyl;

[0050] The malononitrile compounds of formula (Y) wherein R⁵ is halogen,n is an integer of 0 to 2;

[0051] The malononitrile compounds of formula (Y) wherein R⁶ is halogen,cyano, nitro, C₁-C₄ haloalkyl, C₁-C₄ haloalkyloxy, or C₁-C₄,haloalkylthio;

[0052] The malononitrile compounds of formula (Y) wherein R⁵ is halogen,n is an integer of 0 to 2 and R⁶ is halogen, cyano, nitro, C₁-C₄(halo)alkyl, C₁-C₄ (halo)alkyloxy, or C₁-C₄ (halo)alkylthio;

[0053] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 1, and R⁶ is trifluoromethyl;

[0054] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 1, and R⁶ is difluoromethoxy;

[0055] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 1, and R⁶ is trifluoromethoxy;

[0056] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 1, and R⁶ is trifluoromethylthio;

[0057] The malononitrile compounds of formula (wherein R³ iscyclopropyl, m is 1, and R⁶ is 1,1,2,2-tetrafluoroethoxy;

[0058] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 1, and R⁶ is chlorine;

[0059] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 1, and R⁶ is bromine;

[0060] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 1, and R⁶ is fluorine;

[0061] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 1, and R⁶ is cyano;

[0062] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 1, and R⁶ is nitro;

[0063] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 1, and R⁶ is trifluoromethyl;

[0064] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 1, and R⁶ is difluoromethoxy;

[0065] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 1, and R⁶ is trifluoromethoxy;

[0066] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 1, and R⁶ is trifluoromethylthio;

[0067] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 1, and R⁶ is 1,1,2,2-tetrafluoroethoxy;

[0068] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 1, and R⁶ is chlorine;

[0069] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 1, and R⁶ is bromine;

[0070] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 1, and R⁶ is fluorine;

[0071] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 1, and R⁶ is cyano;

[0072] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 1, and R⁶ is nitro;

[0073] The malononitrile compounds of formula (Y) wherein R³ is2,2-dichloro-1-cyclopropyl, m is 1, and R⁶ is trifluoromethyl;

[0074] The malononitrile compounds of formula (Y) wherein R³ is2,2-dichloro-1-cyclopropyl, m is 1, and R⁶ is trifluoromethoxy;

[0075] The malononitrile compounds of formula (Y) wherein R³ is2,2-dichloro-1-cyclopropyl, m is 1, and R⁶ is trifluoromethylthio;

[0076] The malononitrile compounds of formula (Y)-wherein R³ is2,2-dichloro-1-cyclopropyl, m is 1, and R⁶ is chlorine;

[0077] The malononitrile compounds of formula (Y) wherein R³ is2,2-dichloro-1-cyclopropyl, m is 1, and R⁶ is cyano;

[0078] The malononitrile compounds of formula (Y) wherein R³ is2,2-dichloro-1-cyclopropyl, m is 1, and R⁶ is nitro;

[0079] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclopropyl, m is 1, and R⁶ is trifluoromethyl;

[0080] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclopropyl, m is 1, and R⁶ is trifluoromethoxy;

[0081] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclopropyl, m is 1, and R⁶ is trifluoromethylthio;

[0082] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclopropyl, m is 1, and R⁶ is chlorine;

[0083] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclopropyl, m is 1, and R⁶ is cyano;

[0084] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclopropyl, m is 1, and R⁶ is nitro;

[0085] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 2, and R⁶ is trifluoromethyl;

[0086] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 2, and R⁶ is trifluoromethoxy;

[0087] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 2, and R⁶ is trifluoromethylthio;

[0088] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is −2, and R⁶ is chlorine;

[0089] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 2, and R⁶ is bromine;

[0090] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 2, and R⁶ is fluorine;

[0091] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 2, and R⁶ is cyano;

[0092] The malononitrile compounds of formula (Y) wherein R³ iscyclopropyl, m is 2, and R⁶ is nitro;

[0093] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 2, and R⁶ is trifluoromethyl;

[0094] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 2, and R⁶ is trifluoromethoxy;

[0095] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 2, and R⁶ is trifluoromethylthio;

[0096] The malononitrile compounds of formula (Y) wherein R³iscyclobutyl; m is 2, and R⁶ is chlorine;

[0097] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 2, and R⁶ is bromine;

[0098] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 2, and R⁶ is fluorine;

[0099] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 2, and R⁶ is cyano;

[0100] The malononitrile compounds of formula (Y) wherein R³ iscyclobutyl, m is 2, and R⁶ is nitro;

[0101] The malononitrile compounds of formula (Y) wherein R³ is2-2-dichloro-1-cyclobutyl, m is 2, and R⁶ is trifluoromethyl;

[0102] The malononitrile compounds of formula (Y) wherein R³ is2,2-dichloro-1-cyclobutyl, m is 2, and R⁶ is trifluoromethoxy;

[0103] The malononitrile compounds of formula (Y) wherein R³ is2,2-dichloro-1-cyclobutyl, m is 2, and R⁶ is trifluoromethylthio;

[0104] The malononitrile compounds of formula (Y) wherein R³ is2,2-dichloro-1-cyclobutyl, m is 2, and R⁶ is chlorine;

[0105] The malononitrile compounds of formula (Y) wherein R³ is2,2-dichloro-1-cyclobutyl, m is 2, and R⁶ is bromine;

[0106] The malononitrile compounds of formula (Y) wherein R³ is2,2-dichloro-1-cyclobutyl, m is 2, and R⁶ is fluorine;

[0107] The malononitrile compounds of formula (Y) wherein R³ is2,2-dichloro-1-cyclobutyl, m is 2, and R⁶ is cyano;

[0108] The malononitrile compounds of formula (Y) wherein R³ is2,2-dichloro-1-cyclobutyl, m is 2, and R⁶ is nitro;

[0109] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclobutyl, m is 2, and R⁶ is trifluoromethyl;

[0110] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclobutyl, m is 2, and R⁶ is trifluoromethoxy;

[0111] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclobutyl, m is 2, and R⁶ is trifluoromethylthio;

[0112] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclobutyl, m is 2, and R⁶ is chlorine;

[0113] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclobutyl, m is 2, and R⁶ is bromine;

[0114] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclobutyl, m is 2, and R⁶ is fluorine;

[0115] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclobutyl, m is 2, and R⁶ is cyano;

[0116] The malononitrile compounds of formula (Y) wherein R³ is2,2-difluoro-1-cyclobutyl, m is 2, and R⁶ is nitro.

[0117] The following will describe the production processes for thepresent compounds.

[0118] The preferred compounds among the present compounds are thecompounds wherein R⁶ is halogen, cyano, nitro, C₁-C₄ haloalkyl, C₁-C₄haloalkyloxy or C₁-C₄ haloalkylthio; or the compounds wherein n is 1 to3 and at least one of R⁵ is halogen, cyano, nitro, C₁-C₄ haloalkyl,C₁-C₄ haloalkyloxy or C₁-C₄ (halo)alkylthio. More preferred compoundsare the compounds wherein R⁶ is halogen, cyano, nitro, C₁-C₄fluoroalkyl, C₁-C₄ fluoroalkyloxy or C₁-C₄ fluoroalkylthio; or thecompounds wherein n is 1 to 3 and at least one of R⁵ is halogen, cyano,nitro, C₁-C₄ fluoroalkyl, C₁-C₄ fluoroalkyloxy or C₁-C₄ fluoroalkylthio.

[0119] The present compounds can be produced by, for example, thefollowing (Production Process 1) or (Production Process 2).

[0120] (Production Process 1)

[0121] This is a process by reacting compound (a) with compound (b) inthe presence of a base.

[0122] wherein R¹, R², R³, R⁵, R⁶, m, and n are as defined above, and Zis halogen, methanesulfonyl, trifluoromethanesulfonyl, ortoluenesulfonyl.

[0123] The reaction is usually carried out in a solvent. The solventwhich can be used in the reaction may include acid amides such asdimethylformamide; ethers such as diethyl ether and tetrahydrofuran;organic sulfur compounds such as dimethylsulfoxide and sulfolane;halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene;aromatic hydrocarbons such as toluene and xylene; water; and mixturesthereof.

[0124] The base which can be used in the reaction may include inorganicbases such as sodium hydride, sodium hydroxide, potassium hydroxide, andpotassium carbonate; alkali metal alkoxides such as sodium methoxide,sodium ethoxide, and potassium tert-butoxide; alkali metal amides suchas lithium diisopropylamide; and organic bases such as4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, and1,8-diazabicylco[5.4.0]-7-undecene. The amount of base used in thereaction is usually in a ratio of 1 to 10 moles relative to 1 mole ofcompound (a).

[0125] The reaction temperature is usually in the range of −20° C. to100° C.

[0126] The reaction time is usually in the range of 1 to 24 hours.

[0127] The amount of compound (b) used in the reaction is usually in aratio of 1 to 10 moles relative to 1 mole of compound (a).

[0128] After the reaction, the reaction mixture is poured into water,followed by ordinary post-treatment procedures including extraction withan organic solvent and concentration, thereby isolating the desiredpresent compounds, which may be purified by a technique such aschromatography or recrystallization.

[0129] (Production Process 2)

[0130] This is a process by reacting compound (c) with compound (d) inthe presence of a base.

[0131] wherein R¹, R², R³, R⁵, R⁶, m, n, and Z are as defined above.

[0132] The reaction is usually carried out in a solvent. The solventwhich can be used in the reaction may include acid amides such asdimethylformamide; ethers such as diethyl ether and tetrahydrofuran;organic sulfur compounds such as dimethylsulfoxide and sulfolane;halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene;aromatic hydrocarbons such as toluene and xylene; water; and mixturesthereof.

[0133] The base which can be used in the reaction may include inorganicbases such as sodium hydride, sodium hydroxide, potassium hydroxide, andpotassium carbonate; alkali metal alkoxides such as sodium methoxide,sodium ethoxide, and potassium tert-butoxide; alkali metal amides suchas lithium diisopropylamide; and organic bases such as4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, and1,8-diazabicylco[5.4.0]-7-undecene. The amount of base used in thereaction is usually in a ratio of 1 to 10 moles relative to 1 mole ofcompound (a).

[0134] The reaction temperature is usually in the range of −20° C. to100° C.,

[0135] The reaction time is usually in the range of 1 to 24 hours.

[0136] The amount of compound (b) used in the reaction is usually in aratio of 1 to 10 moles relative to 1 mole of compound (a).

[0137] After the reaction, the reaction mixture is poured into water,followed by ordinary post-treatment procedures including extraction withan organic solvent and concentration, thereby isolating the desiredpresent compounds, which may be purified by a technique such aschromatography or recrystallization.

[0138] The compound (a) can be produced through a route, for example, asshown in the following scheme.

[0139] wherein R¹, R², R⁵, R⁶, and n are as defined above.

[0140] (Step 1)

[0141] The compound (f) can be produced by reacting compound (e) withmalononitrile.

[0142] The reaction is usually carried out in a solvent and in thepresence of a base. The solvent which can be used in the reaction mayinclude acid amides such as N,N-dimethylformamide; ethers such asdiethyl ether and tetrahydrofuran; halogenated hydrocarbons such aschloroform, 1,2-dichloroethane, and chlorobenzene; aromatic hydrocarbonssuch as toluene and xylene; alcohols such as methanol, ethanol, andisopropanol; and mixtures thereof.

[0143] The base which can be used in the reaction may includetetrabutylammonium hydroxide. The amount of base used in the reaction isusually in a ratio of 0.01 to 0.5 mole relative to 1 mole of compound(e).

[0144] The amount of malononitrile used in the reaction is usually in aratio of 1 to 10 moles relative to 1 mole of compound (e).

[0145] The reaction temperature is usually in the range of —20° C. to200° C.

[0146] The reaction time is usually in the range of 1 to 24 hours.

[0147] The reaction may be carried out, while removing, if necessary,water which is generated by the reaction, from the reaction system.

[0148] After the reaction, the reaction mixture is poured into water,followed by ordinary post-treatment procedures including extraction withan organic solvent and concentration, thereby isolating the desiredpresent compounds, which may be purified by a technique such aschromatography or recrystallization.

[0149] (Step 2)

[0150] (1) The case where R² is a substituent other than hydrogen andcyano:

[0151] The compound (a) can be produced by reacting compound (f) with anorganometallic compound.

[0152] The reaction is usually carried out in a solvent and, ifnecessary, in the presence of a copper salt.

[0153] The solvent which can be used in the reaction may include etherssuch as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such astoluene and xylene; and mixtures thereof.

[0154] The organometallic compound which can be used in the reaction mayinclude organic magnesium compounds such as methyl magnesium iodide,ethyl magnesium bromide, isopropyl magnesium bromide, vinyl magnesiumbromide, ethynyl magnesium bromide, and dimethyl magnesium; organiclithium compounds such as methyl lithium; organic zinc compounds such asdiethyl zinc; and organic copper compounds such as trifluoromethylcopper. The amount of organometallic compound used in the reaction, isusually in a ratio of 1 to 10 moles relative to 1 mole of compound (f).

[0155] The copper salt which can be used in the reaction may includecopper (I) iodide and copper (I) bromide. The amount of copper salt usedin the reaction is usually not greater than 1 mole relative to 1 mole ofcompound (f).

[0156] The reaction temperature is usually in the range of −20° C. to100° C.

[0157] The reaction time is usually in the range of 1 to 24 hours.

[0158] After the reaction, the reaction mixture is poured into water,followed by ordinary post-treatment procedures including extraction withan organic solvent and concentration, thereby isolating the desiredpresent compounds, which may be purified by a technique such aschromatography or recrystallization.

[0159] (2) The case where R² is hydrogen:

[0160] The compound (a) can be produced by subjecting compound (f) toreduction.

[0161] The reduction is usually carried out in a solvent.

[0162] The solvent which can be used in the reaction may include etherssuch as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such astoluene and xylene; alcohols such as methanol, ethanol, and propanol;water; and mixtures thereof.

[0163] The reducing agent which can be used in the reaction may includesodium borohydride. The amount of reducing agent used in the reaction isusually in a ratio of 0.25 to 2 moles relative to 1 mole of compound(f).

[0164] The reaction time is usually in the range of a moment to 24hours.

[0165] The reaction temperature is usually in the range of 0° C. to 50°C.

[0166] After the reaction, the reaction mixture is poured into water,followed by ordinary post-treatment procedures including extraction withan organic solvent and concentration, thereby isolating the desiredpresent compounds, which may be purified by a technique such aschromatography or recrystallization.

[0167] (3) The case where R² is cyano:

[0168] The compound (a) can be produced by reacting compound (f) with acyanide.

[0169] The solvent which can be used in the reaction may include etherssuch as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such astoluene and xylene; and mixtures thereof.

[0170] The cyanide which can be used in the reaction may includetetrabutylammonium cyanide. The amount of cyanide used in the reactionis usually in a ratio of 1 to 10 moles relative to 1 mole of compound(f).

[0171] The reaction temperature is usually in the range of −20° C. to100° C.

[0172] The reaction time is usually in the range of 1 to 24 hours.

[0173] After the reaction, the reaction mixture is poured into water,followed by ordinary post-treatment procedures including extraction withan organic solvent and concentration, thereby isolating the desiredpresent compounds, which may be purified by a technique such aschromatography or recrystallization.

[0174] The pests against which the present compounds exhibit controllingactivity may include insect pests, acarine pests, and nematode pests,specific examples which are as follows:

[0175] Hemiptera:

[0176] Delphacidae such as Laodelphax striatellus, Nilaparvata lugens,and Sogatella furcifera;

[0177] Deltocephalidae such as Nephotettix cincticeps and Nephotettixvirescens;

[0178] Aphididae such as Aphis gossypii and Myzus persicae;

[0179] Pentatomidae such as Nezara antennata, Riptortus clavetus,Eysarcoris lewisi, Eysarcoris parvus, Plautia stali and Halyomorphamisia;

[0180] Aleyrodidae such as Trialeurodes vaporariorum and Bemisiaargentifolir;

[0181] Coccidae such as Aonidiella aurantii, Comstockaspis perniciosa,Unaspis citri, Ceroplastes rubens, and Icerya purchasi;

[0182] Tingidae;

[0183] Psyllidae;

[0184] Lepidoptera:

[0185] Pyralidae such as Chilo suppressalis, Cnaphalocrocis medinalis,Notarcha derogata, and Plodia interpunctella;

[0186] Noctuidae such as Spodoptera litura, Pseudaletia separata,Thoricoplusia spp., Heliothis spp., and Helicoverpa spp.;

[0187] Pieridae such as Pieris rapae;

[0188] Tortricidae such as Adoxophyes spp., Grapholita molesta, andCydia pomonella;

[0189] Carposinidae such as Carposina niponensis;

[0190] Lyonetiidae such as Lyonetia spp.;

[0191] Lymantriidae such as Lyamantria spp. and Euproctis spp.;

[0192] Yponomentidae such as Plutella xylostella;

[0193] Gelechiidae such as Pectinophora gossypiella;

[0194] Arctiidae such as Hyphantria cunea;

[0195] Tineidae such as Tinea translucens and Tineola bisselliella;

[0196] Diptera:

[0197] Calicidae such as Culex pipiens pallens, Culex tritaeniorhynchus,and Culex quinquefasciatus;

[0198] Aedes spp. such as Aedes aegypti and Aedes albopictus;

[0199] Anopheles spp. such as Anopheles sinensis;

[0200] Chironomidae;

[0201] Muscidae such as Musca domestica and Muscina stabulans;

[0202] Calliphoridae;

[0203] Sarcophagidae;

[0204] Fanniidae;

[0205] Anthomyiidae such as Delia platura and Delia antiqua;

[0206] Tephritidae;

[0207] Drosophilidae;

[0208] Psychodidae;

[0209] Simuliidae;

[0210] Tabanidae;

[0211] Stomoxyidae;

[0212] Agromyzidae;

[0213] Coleoptera:

[0214] Diabrotica spp. such as Diabrotica virgifera and Diabroticaundecimpunctata howardi;

[0215] Scarabaeidae such as Anomala cuprea and Anomala rufocuprea;

[0216] Curculionidae such as Sitophilus zeamais, Lissorhoptrusoryzophilus, and Callosobruchuys chienensis;

[0217] Tenebrionidae such as Tenebrio molitor and Tribolium castaneum;

[0218] Chrysomelidae such as Oulema oryzae, Aulacophora femoralis,Phyllotreta striolata, and Leptinotarsa decemlineata;

[0219] Anobiidae;

[0220] Epilachna spp. such as Epilachna vigintioctopunctata;

[0221] Lyctidae;

[0222] Bostrychidae;

[0223] Cerambycidae;

[0224]Paederus fuscipes;

[0225] Dictyoptera:

[0226]Blattella germanica, Periplaneta fuliginosa, Periplanetaamericana, Periplaneta brunnea, and Blatta orientalis;

[0227] Thysanoptera:

[0228]Thrips palmi, Thrips tabaci, Frankliniella occidentals,Frankliniella intonsa;

[0229] Hymenoptera:

[0230] Formicidae;

[0231] Vespidae;

[0232] Bethylidae;

[0233] Tenthredimidae such as Athalia japonica;

[0234] Orthoptera:

[0235] Gryllotalpidae;

[0236] Acrididae;

[0237] Siphonaptera:

[0238]Ctenocephalides felis, Ctenocephalides canis, Pulex irritans,Xenopsylla cheopis;

[0239] Anoplura:

[0240]Pediculus humanus corporis, Phthirus pubis, Haematopinuseurysternus, and Dalmalinia ovis;

[0241] Isoptera:

[0242]Reticulitermes speratus and Coptotermes formosanus;

[0243] Acarina:

[0244] Tetranychidae such as Tetranychus urticae, Tetranychus kanzawai,Panonychus citri, Panonychus ulmi, and Oligonychus spp.;

[0245] Eriophyidae such as Aculops pelekassi and Aculus schlechtendali;

[0246] Tarsonemidae such as Polyphagotarsonemus latus;

[0247] Tenuipalpidae;

[0248] Tuckerellidae;

[0249] Ixodidae such as Haemaphysalis longicornis, Haemaphysalis flava,Dermacentor taiwanicus, Ixodes ovatus, Ixodes persulcatus, and Boophilusmicroplus;

[0250] Acaridae such as Tyrophagus putrescentiae;

[0251] Epidermoptidae such as Dermatophagoides farinae andDermatophagoides ptrenyssnus;

[0252] Cheyletidae such as Cheyletus eruditus, Cheyletus malaccensis,and Cheyletus moorei;

[0253] Dermanyssidae;

[0254] Arachnida:

[0255]Chiracanthium japonicum and Latrodectus hasseltii;

[0256] Chilopoda:

[0257]Thereuonema hilgendorfi and Scolopendra subspinipes;

[0258] Diplopoda:

[0259]Oxidus gracilis and Nedyopus tambanus;

[0260] Isopoda:

[0261]Armadillidium vulgare;

[0262] Gastropoda:

[0263]Limax marginatus and Limax flavus;

[0264] Nematoda:

[0265]Pratylenchus coffeae, Pratylenchus fallax, Heterodera glycines,Globodera rostochiensis, Meloidogyne hapla, and Meloidogyne incognita.

[0266] When the present compounds are used as the active ingredients ofpesticide compositions, they may be used as such without addition of anyother ingredients. However, they are usually used in admixture withsolid carriers, liquid carriers and/or gaseous carriers, and ifnecessary, by addition of adjuvants such as surfactants, followed byformulation into various forms such emulsifiable concentrates, oilformulations, flowables, dusts, wettable powders, granules, pasteformulations, microcapsule formulations, foams, aerosol formulations,carbon dioxide gas formulations, tablets, or resin formulations. Theseformulations may be used by processing into poison baits, shampoo,mosquito coils, electric mosquito mats, smokes, fumigants, or sheets.

[0267] In these formulations, the present compounds are usuallycontained each in an amount of 0.1% to 95% by weight.

[0268] The solid carrier which can be used in the formulation mayinclude the following materials in fine powder or granular form: clays(e.g., kaolin clay, diatomaceous earth, bentonite, Fubasami clay, acidclay); talc, ceramic, and other inorganic minerals (e.g., sericite,quartz, sulfur, activated carbon, calcium carbonate, hydrated silica);and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate,ammonium nitrate, ammonium chloride, urea).

[0269] The liquid carrier may include aromatic or aliphatic hydrocarbons(e.g., xylene, toluene, alkylnaphthalene, phenylxylylethane, kerosine,light oils, hexane, cyclohexane); halogenated hydrocarbons (e.g.,chlorobenzene, dichloromethane, dichloroethane, trichloroethane);alcohols (e.g., methanol, ethanol, isopropyl alcohol, butanol, hexanol,ethylene glycol); ethers (e.g., diethyl ether, ethylene glycol dimethylether, diethylene glycol monomethyl ether, diethylene glycol monoethylether, propylene glycol monomethyl ether, tetrahydrofuran, dioxane);esters (e.g., ethyl acetate, butyl acetate); ketones (e.g, acetone,methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone); nitrites(acetonitrile, isobutyronitrile); sulfoxides (e.g., dimethylsulfoxide);acid amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide);vegetable oils (e.g., soy bean oil and cotton seed oil); plant essentialoils (eg., orange oil, hyssop oil, lemon oil); and water.

[0270] The gaseous carrier may include butane gas, Freon gas, liquefiedpetroleum gas (LPG), dimethyl ether, and carbon dioxide.

[0271] The surfactant may include alkyl sulfate salts; alkylsulfonicacid salts; alkylarylsulfonic acid salts; alkyl aryl ethers and theirpolyoxyethylene derivatives; polyethylene glycol ethers; polyol esters;and sugar alcohol derivatives.

[0272] The other adjuvants may include binders, dispersants, andstabilizers, specific examples of which are casein, gelatin,polysaccharides (e.g., starch, gum arabic, cellulose derivatives,alginic acid), lignin derivatives, bentonite, sugars, syntheticwater-soluble polymers (e.g., polyvinyl alcohol, polyvinylpyrrolidone,polyacrylic acid), PAP (isopropyl acid phosphate), BHT(2,6-di-t-butyl-4-methylphenol), BHA (mixtures of2-t-butyl-4-methoxyphenol and 3-t-butyl-4-methoxyphenol), vegetableoils, mineral oils, fatty acids, and fatty acid esters.

[0273] The base material for resin formulations may include vinylchloride polymers and polyurethanes. These base materials may contain,if necessary, plasticizers such as phthalic acid esters (e.g., dimethylphthalate, dioctyl phthalate), adipic acid esters, and stearic acid. Theresin formulations can be obtained by kneading the present compoundsinto the base materials with an ordinary kneader and subsequent formingsuch as injection molding, extrusion, or pressing. They can beprocessed, if necessary, though further forming and cutting into resinformulations in various shapes such as plates, films, tapes, nets, orstrings. These resin formulations are processed as, for example, collarsfor animals, ear tags for animals, sheet formulations, attractivestrings, or poles for horticultural use.

[0274] The base material for poison baits may include grain powders,vegetable oils, sugars, and crystalline cellulose. If necessary,additional agents may be added, including antioxidants such asdibutylhydroxytoluene and nordihydroguaiaretic acid; preservatives suchas dehydroacetic acid; agents for preventing children and pets fromerroneously eating, such as hot pepper powder; and pest-attractiveflavors such as cheese flavor, onion flavor, and peanut oil.

[0275] The pesticide compositions of the present invention may be usedby, for example, direct application to pests and/or application to thehabitats of pests (e.g., plant bodies, animal bodies, soil).

[0276] When the pesticide compositions of the present invention-are usedfor the control of pests in agriculture and forestry, their applicationamounts are usually 1 to 10,000 g/ha, preferably 10 to 500 g/ha.Formulations such as emulsifiable concentrates, wettable powders,flowables, and microcapsule formulations are usually used after dilutionwith water to have an active ingredient concentration of 1 to 1000 ppm,while formulations such as dusts and granules are usually used as such.These formulations may be directly applied to plants to be protectedfrom pests. These formulations can also be incorporated into soil forthe control of pests inhabiting the soil, or can also be applied to bedsbefore planting or applied to planting holes or plant bottoms in theplanting. Further, the pesticide compositions of the present inventionin the form of sheet formulations can be applied by the methods in whichthe sheet formulations are wound around plants, disposed in the vicinityof plants, or laid on the soil surface at the plant bottoms.

[0277] When the pesticide compositions of the present invention are usedfor the prevention of epidemics, their application amounts as activeingredient amounts are usually 0.001 to 10 mg/m³ for spatial applicationor 0.001 to 100 mg/m² for planar application. Formulations such asemulsifiable concentrates, wettable powders, and flowables are usuallyapplied after dilution with water to have an active ingredientconcentration of 0.01 to 10,000 ppm, while formulations such as oilformulations, aerosols, smokes or poison baits are usually applied assuch.

[0278] When the pesticide compositions of the present invention are usedfor the control of external parasites on domestic animals such ascattle, sheep, goat, and fowl or small animals such as dogs, cats, rats,and mice, they can be used by the veterinarily well-known methods. Asthe specific methods of use, administration is achieved by, for example,tablets, feed incorporation, suppositories, or injections (e.g.,intramuscular, subcutaneous, intravenous, intraperitoneal) for systemiccontrol, or by, for example, spraying, pour-on treatment, or spot-ontreatment with an oil formulation or an aqueous solution, washinganimals with a shampoo formulation, or attachment of a collar or ear tagprepared from a resin formulation to animals for non-systemic control.The amounts of the present compounds when administered to animal bodiesare usually in the range of 0.1 to 1000 mg per 1 kg weight of eachanimal.

[0279] The pesticide compositions of the present invention can also beused in admixture or combination with other insecticides, nematocides,acaricides, bactericides, fungicides, herbicides, plant growthregulators, synergists, fertilizers, soil conditioners, animal feeds,and the like.

[0280] Examples of the insecticides and acaricides includeorganophosphorus compounds such as fenitrothion [O,O-dimethylO-(3-methyl-4-nitrophenyl) phosphorothioate], fenthion [O,O-dimethylO-(3-methyl-4-(methylthio)phenyl) phosphorothioate], diazinon[O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate],chlorpyrifos [O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate],DDVP [2,2-dichlorovinyl dimethylphosphate], cyanophos [O-4-cyanophenylO,O-dimethyl phosphorothioate], dimethoate [O,O-dimethylS-(N-methylcarbamoylmethyl) dithiophosphate], phenthoate [ethyl2-dimethoxyphosphinothioylthio(phenyl)acetate], malathion [diethyl(dimethoxyphosphinothioylthio)succinate], and azinphosmethyl[S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethylO,O-dimethylphosphorodithioate]; carbamate compounds such as BPMC(2-sec-butylphenyl methylcarbamate), benfracarb [ethylN-[2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio]-N-isopropyl-β-alaninate],propoxur [2-isopropoxyphenyl N-methylcarbamate] and carbaryl [1-naphthylN-methylcarbamate]; pyrethroid compounds such as etofenprox[2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether], fenvalerate[(RS)-α-cyano-3-phenoxybenzyl(RS)-2-(4-chlorophenyl)-3-methyl-butyrate],esfenvalerate[(S)-α-cyano-3-phenoxybenzyl(S)-2-(4-chlorophenyl)-3-methylbutyrate],fenpropathrin [(RS)-α-cyano-3-phenoxybenzyl2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin[(RS)-α-cyano-3-phenoxybenzyl(1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],permethrin [3-phenoxybenzyl(1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],cyhalothrin [(RS)-α-cyano-3-phenoxybenzyl(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate],deltamethrin [(S)-α-cyano-3-phenoxy-benzyl(1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-carboxylate],cycloprothrin [(RS)-α-cyano-3-phenoxybenzyl(RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate],fluvalinate [α-cyano-3-phenoxybenzylN-(2-chloro-α,α,α-trifluoro-p-tolyl)-D-valinate], bifenthrin[2-methylbiphenyl-3-ylmethyl(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethyl-cyclopropanecarboxylate],2-methyl-2-(4-bromodifluoro-methoxyphenyl)-propyl 3-phenoxybenzyl ether,tralomethrin [(S)-α-cyano-3-phenoxybenzyl(1R-cis)-3-{(1RS)(1,2,2,2-tetrabromoethyl)}-2,2-dimethyl-cyclopropanecarboxylate],silafluofen[(4-ethoxyphenyl){3-(4-fluoro-3-phenoxyphenyl)propyl}-dimethylsilane],d-phenothrin [3-phenoxybenzyl(1R-cis,trans)-chrysanthemate],cyphenothrin[(RS)-α-cyano-3-phenoxybenzyl(1R-cis,trans)-chrysanthemate],d-resmethrin [5-benzyl-3-furylmethyl(1R-cis,trans)-chrysanthemate],acrinathrin[(S)-α-cyano-3-phenoxybenzyl(1R,cis(Z))-2,2-dimethyl-3-{3-oxo-3-(1,1,1,3,3,3-hexafluoropropyloxy)propenyl}cyclopropanecarboxylate],cyfluthrin[(RS)-α-cyano-4-fluoro-3-phenoxybenzyl-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],tefluthrin.[2,3,5,6-tetrafluoro-4-methylbenzyl(1RS-cis(Z))-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate],transfluthrin [2,3,5,6-tetrafluorobenzyl(1R-trans)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],tetramethrin[3,4,5,6-tetrahydrophthalimidomethyl(1RS)-cis,trans-chrysanthemate],allethrin[(RS)-3-allyl-2-methyl-4-oxocyclopent-2-enyl(1RS)-cis,trans-chrysanthemate],prallethrin [(S)-2-methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyl(1R)-cis,trans-chrysanthemate], empenthrin[(RS)-1-ethynyl-2-methyl-2-pentenyl(1R)-cis,trans-chrysanthemate],imiprothrin [2,5-dioxo-3-(prop-2-ynyl)imidazolidin-1-ylmethyl(1R)-cis,trans-2,2′-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylate],d-furamethrin [5-(2-propynyl) furfuryl (1R)-cis,trans-chrysanthemate]and 5-(2-propynyl)furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate;neonicotinoid derivatives such asN-cyano-N′-methyl-N′-(6-chloro-3-pyridylmethyl)acetamidine; nitenpyram[N-(6-chloro-3-pyridylmethyl)-N-ethyl-N′-methyl-2-nitrovynylidenediamine];thiacloprid [1-(2-chloro-5-pyridylmethyl)-2-cyanoiminothiazoline];thiamethoxam[3-((2-chloro-5-thiazolyl)methyl)-5-methyl-4-nitroiminotetrahydro-1,3,5-oxadiazine],1-methyl-2-nitro-3-((3-tetrahydrofuryl)methyl)guanidine and1-(2-chloro-5-thiazolyl)methyl-3-methyl-2-nitroguanidine;nitroiminohexahydro-1,3,5-triazine derivatives; chlorinated hydrocarbonssuch as endosulfan[6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepineoxide], γ-BHC [1,2,3,4,5,6-hexachlorocyclohexane] and1,1-bis(chlorophenyl)-2,2,2-trichloroethanol; benzoylphenylureacompounds such as chlorfluazuron[1-(3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridyn-2-yloxy)phenyl)-3-(2,6-difluorobenzoyl)urea],teflubenzuron[1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea] andflufenoxuron[1-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)-3-(2,6-difluorobenzoyl)urea];juvenile hormone like compounds such as pyriproxyfen [4-phenoxyphenyl2-(2-pyridyloxy)propyl ether], methoprene [isopropyl(2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate] and hydroprene[ethyl (2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate]; thioureaderivatives such as diafenthiuron[N-(2,6-diisopropyl-4-phenoxyphenyl)-N′-tert-butylcarbodiimide];phenylpyrazole compounds;4-bromo-2-(4-chlorophenyl)-1-ethoxymethyl-5-trifluoromethylpyrrol-3-carbonitrile[chlorfenapil]; metoxadiazone[5-methoxy-3-(2-methoxyphenyl)-1,3,4-oxadiazol-2(3H)-one],bromopropylate [isopropyl 4,4′-dibromobenzilate], tetradifon[4-chlorophenyl 2,4,5-trichlorophenyl sulfone], chinomethionat[S,S-6-methylquinoxaline-2,3-diyldithiocarbonate], pyridaben[2-tert-butyl-5-(4-tertbutylbenzylthio)-4-chloropyridazin-3(2H)-one],fenpyroximate [tert-butyl(E)-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate],tebufenpyrad[N-(4-tert-butylbenzyl)-4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide],polynactins complex [tetranactin, dinactin and trinactin], pyrimidifen[5-chloro-N-[2-{4-(2-ethoxyethyl)-2,3-dimethylphenoxy}ethyl]-6-ethylpyrimidin-4-amine],milbemectin, abamectin, ivermectin and azadirachtin [AZAD]. Examples ofthe synergists include bis-(2,3,3,3-tetrachloropropyl)ether (S-421),N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (MGK-264) andα-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene(piperonyl butoxide).

[0281] The present invention will further be illustrated by thefollowing production examples, formulation examples, and test examples;however, the present invention is not limited only to these examples. Inthe formulation examples, the present compound numbers are those shownin Table 1 below.

[0282] The following will describe some production examples for thepresent compounds.

PRODUCTION EXAMPLE 1

[0283] First, 0.50 g of (4-chlorobenzyl)malononitrile was dissolved in 5ml of N,N-dimethylformamide, to which 160 mg of sodium hydride (60% inoil) was added under ice cooling. After the evolution of hydrogen gasceased, while stirring under ice cooling, 0.51 ml ofbromomethylcyclopropane was added dropwise, followed by stirring at roomtemperature overnight. Then, 10% hydrochloric acid was added to thereaction mixture, which was extracted with diethyl ether. The organiclayer was successively washed with 10% hydrochloric acid, a saturatedaqueous sodium chloride solution, dried over anhydrous magnesiumsulfate, and then concentrated under reduced pressure. The residue wassubjected to silica gel column chromatography to give 0.20 g of2-(4-chlorobenzyl)-2-(cyclopropylmethyl)malononitrile (the presentcompound (1)).

[0284] Yield: 31%;

[0285] n_(D) ^(24.5):1.5321.

PRODUCTION EXAMPLE 2

[0286] Using 0.20 g of (4-(trifluoromethoxy)benzyl)malononitrile, 5 mlof N,N-dimethylformamide, 50 mg of sodium hydride (60% in oil), and 0.16ml of bromomethylcyclopropane, and according to the process described inthe Production Example 1, there was obtained 55 mg of2-(cyclopropylmethyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile (thepresent compound (2)).

[0287] Yield: 23%;

[0288] n_(D) ^(24.5):1.4719.

PRODUCTION EXAMPLE 3

[0289] Using 0.50 g of (4-(trifluoromethoxy)benzyl)malononitrile, 6 mlof N,N-dimethylformamide, 92 mg of sodium hydride (60% in oil), and 0.41g of bromomethylcyclobutane, and according to the process described inthe Production Example 1, there was obtained 0.13 g of2-(cyclobutylmethyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile (thepresent compound (3)).

[0290] Yield: 20%;

[0291]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.76-2.04 (4H, m), 2.08 (2H, d),2.19-2.33 (2H, m), 2.64-2.85 (1H, m), 3.16 (2H, s), 7.26 (2H, d), 7.40(2H, d).

PRODUCTION EXAMPLE 4

[0292] Using 0.50 g of (4-(trifluoromethylthio)benzyl)malononitrile, 6ml of N,N-dimethylformamide, 90 mg of sodium hydride (60% in oil), and0.35 g of bromomethylcyclobutane, and according to the process describedin the Production Example 1, there was obtained 0.14 g of2-(cyclobutylmethyl)-2-(4-(trifluoromethylthio)benzyl)malononitrile (thepresent compound (4)).

[0293] Yield: 22%;

[0294]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.73-2.05 (4H, m), 2.07 (2H, d),2.19-2.32 (2H, m), 2.64-2.83 (1H, m), 3.18 (2H, s), 7.43 (2H, d), 7.69(2H, d).

PRODUCTION EXAMPLE 5

[0295] Using 0.50 g of (4-(trifluoromethoxy)benzyl)malononitrile, 9 mlof N,N-dimethylformamide, 96 mg of sodium hydride (60% in oil), and 0.85g of 1-bromomethyl-2,2-dichlorocyclopropane, and according to theprocess described in the Production Example 1, there was obtained 0.37 gof2-((2,2-dichlorocyclopropyl)methyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile(the present compound (5)).

[0296] Yield: 49%;

[0297]¹H-NMR (CDCl₃, TMS, 6 (ppm)): 1.41-1.51 (1H, m), 1.87-2.02 (2H,m), 2.04-2.12 (1H, m), 2.51-2.57 (1H, m), 3.27 (2H, s), 7.28 (2H, d),7.44 (2H, d).

PRODUCTION EXAMPLE 6

[0298] Using 0.50 g of (4-(trifluoromethyl)benzyl)malononitrile, 21 mlof N,N-dimethylformamide, 100 mg of sodium hydride (60% in oil), and0.45 g of bromomethylcyclopropane, and according to the processdescribed in the Production Example 1, there was obtained 0.17 g of2-(cyclopropylmethyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (thepresent compound (6)).

[0299] Yield: 28%;

[0300]¹H-NMR (CDCl₃, TMS, δ (ppm)): 0.37-0.43 (2H, m), 0.72-0.78 (2H,m), 1.01-1.19(1H, m), 1.96 (2H, d), 3.28(2H, s), 7.52 (2H, d), 7.68 (2H,d).

PRODUCTION EXAMPLE 7

[0301] Using 0.30 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.06 g of sodium hydride (60% in oil), and 0.24 gof bromomethylcyclobutane, and according to the process described in theProduction Example 1, there was obtained 97 mg of2-(cyclobutylmethyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (thepresent compound (7)).

[0302] Yield: 25%;

[0303]¹H-NMR (CDCl₃;TMS, δ (ppm)): 1.72-2.04(4H, m), 2.02(2H, d),2.12-2.27(2H, m), 2.64-2.77(1H, m), 3.14(2H, s), 7.43(2H, d), 7.61(2H,d).

PRODUCTION EXAMPLE 8

[0304] Using 0.37 g of (4-cyanobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 0.32 gof 2-bromomethyl-1,1-dichlorocyclopropane, and according to the processdescribed in the Production Example 1, there was obtained 0.29 g of2-(4-cyanobenzyl)-2-((2,2-dichlorocyclopropyl)methyl)malononitrile (thepresent compound (9)).

[0305] Yield: 47%;

[0306]¹H-NMR (CDCl₃, TMS, δ (ppm)):1.43-1.51(1H,m), 1.90-1.99(2H,m),2.10-2.19(1H, m)>2.53-2.58(1H, m), 3.32(2H, s), 7.62(2H, d)>7.76(2H, d).

PRODUCTION EXAMPLE 9

[0307] Using 0.45 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.41 gof 2-bromomethyl-1,1-dichlorocyclopropane, and according to the processdescribed in the Production Example 1, there was obtained2-((2,2-dichlorocyclopropyl)methyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(the present compound (10)).

[0308]¹H-NMR (CDCl₃, TMS, 6 (ppm)): 1.45-1.48 (1H, m), 1.89-1.97 (2H,m), 2.07-2.14 (1H, m), 2.52-2.58 (1H, m), 3.33 (2H, s), 7.54 (2H, d),7.71 (2H, d).

[0309] The following will describe some production examples forintermediate compounds as reference production examples.

REFERENCE PRODUCTION EXAMPLE 1

[0310] First, 1.00 g of (4-chloro-α-methylbenzylidene)malononitrile ofthe formula:

[0311] was dissolved in 20 ml of diethyl ether, to which a catalyticamount of copper (I) iodide was added, and while stirring under icecooling, a solution of methyl magnesium iodide in diethyl ether(prepared from 0.30 g of magnesium, 10 ml of diethyl ether, and 0.86 mlof methyl iodide) was added dropwise, followed by stirring for 30minutes under ice cooling. Then, 10% hydrochloric acid was added to thereaction mixture, which was extracted with ethyl ether. The organiclayer was successively washed with 10% hydrochloric acid, a saturatedaqueous sodium chloride solution, dried over anhydrous magnesiumsulfate, and then concentrated under reduced pressure. The residue wassubjected to silica gel column chromatography to give 0.74 g of(1-(4-chlorophenyl)-1-methylethyl)malononitrile (the intermediate (2)).

[0312] Yield: 69%.

REFERENCE PRODUCTION EXAMPLE 2

[0313] First, 1.02 g of (4-chlorobenzylidene)malononitrile was dissolvedin 20 ml of tetrahydrofuran, to which a catalytic amount of copper (I)iodide was added, and while stirring under ice cooling, a solution ofisopropyl magnesium bromide in tetrahydrofuran (prepared from 0.34 g ofmagnesium, 10 ml of tetrahydrofuran, and 1.46 ml of isopropyl bromide)was added dropwise, followed by stirring for 30 minutes under icecooling. Then, 10% hydrochloric acid was added to the reaction mixture,which became acidic and was extracted with ethyl ether. The organiclayer was successively washed with 10% hydrochloric acid, a saturatedaqueous sodium chloride solution, dried over anhydrous magnesiumsulfate, and then concentrated under reduced pressure. The residue wassubjected to silica gel column chromatography to give 0.66 g of(1-(4-chlorophenyl)-2-methylpropyl)malononitrile (the intermediate (3)).

[0314] Yield: 52%.

REFERENCE PRODUCTION EXAMPLE 3

[0315] First, 4.44° g of (4-(trifluoromethyl)benzylidene)malononitrilewas dissolved in 20 ml of ethanol, and while stirring at roomtemperature, a suspension of 0.19 g of sodium borohydride in 5 ml ofethanol was added dropwise, followed by stirring at room temperature for30 minutes. Then, 10% hydrochloride acid was added to the reactionmixture, which became acidic and was extracted with diethyl ether. Theorganic layer was successively washed with 10% hydrochloric acid, asaturated aqueous sodium chloride solution, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresidue was subjected to silica gel column chromatography to give 2.30 gof (4-(trifluoromethyl)benzyl)malononitrile (the intermediate (4)).

[0316] Yield: 51%.

REFERENCE PRODUCTION EXAMPLE 4

[0317] First, 3.00 g of (4-chloro-α-methylbenzylidene)malononitrile wasdissolved in 20 ml of ethanol, and while stirring at room temperature, asuspension of 0.15 g of sodium borohydride in 5 ml of ethanol was addeddropwise, followed by stirring at room temperature for 30 minutes. Then,10% hydrochloride acid was added to the reaction mixture, which wasextracted with diethyl ether. The organic layer was successively washedwith 10% hydrochloric acid, a saturated aqueous sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 1.70 g of (1-(4-chlorophenyl)ethyl)malononitrile(the intermediate (6)).

[0318] Yield: 56%.

REFERENCE PRODUCTION EXAMPLE 5

[0319] First, 10.0 g of 4-(trifluoromethoxy)benzaldehyde and 3.50 g ofmalononitrile were dissolved in 60 ml of 70% (w/w) aqueous ethanol, towhich a catalytic amount of benzyltrimethylammonium hydroxide was added,and the mixture was stirred at room temperature overnight. Then, asaturated aqueous sodium chloride solution was added to the reactionmixture, which was extracted with ethyl acetate. The organic layer waswashed with a saturated aqueous sodium chloride solution, dried overanhydrous magnesium sulfate, and then concentrated under reducedpressure. The residue was recrystallized from t-butyl methyl ether andhexane to give 9.24 g of (4-(trifluoromethoxy)benzylidene)malononitrile.

[0320] Yield: 74%;

[0321]¹H-NMR (CDCl₃, TMS, 6 (ppm)): 7.37 (2H, d), 7.76 (1H, s), 7.98(2H, d).

[0322] Then, 2.61 g. of (4-(trifluoromethoxy)benzylidene)malononitrilewas dissolved in 20 ml of tetrahydrofuran, and while stirring at roomtemperature, a suspension of 0.11 g of sodium borohydride in 5 ml ofethanol was added dropwise, followed by stirring at room temperature for30 minutes. Then, 10% hydrochloric acid was added, and the mixture wasextracted with diethyl ether. The organic layer was successively washedwith 10% hydrochloric acid, a saturated aqueous sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 2.20 g of(4-(trifluoromethoxy)benzyl)malononitrile (the intermediate (7)).

[0323] Yield: 83%.

REFERENCE PRODUCTION EXAMPLE 6

[0324] Using 1.19 g of (4-(trifluoromethoxy)benzylidene)malononitrile,20 ml of tetrahydrofuran, a catalytic amount of copper (I) iodide, and asolution of isopropyl magnesium bromide in tetrahydrofuran (preparedfrom 0.39 g of magnesium, 10 ml of tetrahydrofuran, and 2.36 g ofisopropyl bromide), and according to the process described in ReferenceProduction Example 2, there was obtained 0.77 g of(1-(4-(trifluoromethoxy)phenyl)-2-methylpropyl)malononitrile (theintermediate (8)).

[0325] Yield: 55%.

REFERENCE PRODUCTION EXAMPLE 7

[0326] Using 1.19 g of (4-(trifluoromethoxy)benzylidene)malononitrile,20 ml of tetrahydrofuran, a catalytic amount of copper (I) iodide, and12.5 ml of a solution of methyl magnesium bromide in tetrahydrofuran(about 1 M, available from Tokyo Kasei Kogyo Co., Ltd), and according tothe process described in Reference Production Example 2, there wasobtained 0.76 g of (1-(4-(trifluoromethoxy)phenyl)ethyl)malononitrile(the intermediate (10)).

[0327] Yield: 60%.

REFERENCE PRODUCTION EXAMPLE 8

[0328] First, 4.46 g of (3,4-dichlorobenzylidene)malononitrile wasdissolved in 20 ml of tetrahydrofuran, and while stirring at roomtemperature, a suspension of 0.19 g of sodium borohydride in 5 ml ofethanol was added dropwise, followed by stirring at room temperature for30 minutes. Then, 10% hydrochloride acid was added and the mixture wasextracted with diethyl ether. The organic layer was successively washedwith 10% hydrochloric acid, a saturated aqueous sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 3.15 g of (3,4-dichlorobenzyl)malononitrile (theintermediate (12)).

[0329] Yield: 70%.

REFERENCE PRODUCTION EXAMPLE 9

[0330] Using 4.46 g of (2,4-dichlorobenzylidene)malononitrile, 20 ml oftetrahydrofuran, and a suspension of 0.19 g of sodium borohydride in 5ml of ethanol, and according to the process described in ReferenceProduction Example 8, there was obtained 3.10 g of(2,4-dichlorobenzyl)malononitrile (the intermediate (13)).

[0331] Yield: 69%.

REFERENCE PRODUCTION EXAMPLE 10

[0332] First, 10.0 g of 4-(trifluoromethylthio)benzaldehyde and 2.92 gof malononitrile were dissolved in 50 ml of 70% (w/w) aqueous ethanol,to which a catalytic amount of benzyltrimethylammonium hydroxide wasadded, and the mixture was stirred at room temperature overnight. Then,a saturated aqueous sodium chloride solution was added to the reactionmixture, which was extracted with ethyl acetate. The organic layer waswashed with a saturated aqueous sodium chloride solution, dried overanhydrous magnesium sulfate, and then concentrated under reducedpressure. The residue was recrystallized with a solvent systemconsisting of t-butyl methyl ether and hexane to give 10.5 g of(4-(trifluoromethylthio)benzylidene)malononitrile.

[0333] Yield: 85%;

[0334]¹H-NMR (CDCl₃, TMS, δ (ppm)): 7.78 (1H, s), 7.79 (2H; d), 7.93(2H, d).

[0335] Then, 8.00 g of (4-(trifluoromethylthio)benzylidene)malononitrileand 3.35 g of benzaldehyde were dissolved in 320 ml of ethanol, andwhile stirring at room temperature, 3.41 g of phenylenediamine wasslowly added, and the mixture was stirred at room temperature for 5hours. Then, the reaction mixture was concentrated, 300 ml of t-butylmethyl ether was added, and insoluble matters were filtered. Thefiltrate was concentrated and the resulting residue was subjected tosilica gel chromatography to give 6.22 g of(4-(trifluoromethylthio)benzyl)malononitrle (the intermediate (14)).

[0336] Yield: 77%.

REFERENCE PRODUCTION EXAMPLE 11

[0337] Using 4.00 g of (4-(trifluoromethoxy)benzylidene)malononitrile,30 ml of tetrahydrofuran, 175 mg of copper (I) bromide dimethyl sulfidecomplex, and 26 ml of a solution (0.98 M) of vinyl magnesium bromide intetrahydrofuran, and according to the process described in ReferenceProduction Example 2, there was obtained 1.60 g of(1-(4-trifluoromethoxyphenyl)-2-propenyl)malononitrile (the intermediate(15)).

[0338] The intermediate compounds used in the production of the presentcompounds are shown below with the compound numbers and physical data.

[0339] Intermediate (1)

[0340] (4-Chlorobenzyl)malononitrile

[0341] m.p.: 96.9° C.

[0342] Intermediate (2)

[0343] (1-(4-Chlorophenyl)-1-methylethyl)malononitrile

[0344] n_(D) ^(22.0):1.5372.

[0345] Intermediate (3)

[0346] (1-(4-Chlorophenyl)-2-methylpropyl)malononitrile

[0347] n_(D) ^(21.5):1.5289.

[0348] Intermediate (4)

[0349] (4-(Trifluoromethyl)benzyl)malononitrile

[0350] m.p.: 79.1° C.

[0351] Intermediate (5)

[0352] (4-Cyanobenzyl)malononitrile

[0353] m.p.: 118.7° C.

[0354] Intermediate (6).

[0355] (1-(4-Chlorophenyl)ethyl)malononitrile

[0356] n_(D) ^(24.5):1.5349.

[0357] Intermediate (7)

[0358] (4-(Trifluoromethoxy)benzyl)malononitrile

[0359] m.p.: 88.3° C.

[0360] Intermediate (8)

[0361] (1-(4-(Trifluoromethoxy)phenyl-2-methylpropyl)malononitrile

[0362]¹H-NMR (CDCl₃, TMS, δ (ppm)): 0.83 (3H, d), 1.16 (3H, d),2.29-2.45 (1H, m), 2.87 (1H, dd), 4.18 (1H, d), 7.25-7.30 (2H, m),7.38-7.42 (2H, m).

[0363] Intermediate (9)

[0364] (4-Bromobenzyl)malononitrile

[0365] m.p.: 97.7° C.

[0366] Intermediate (10)

[0367] (1-(4-(Trifluoromethoxy)phenyl)ethyl)malononitrile

[0368]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.65 (3H, d), 3.49 (1H, dq), 3.85(1H, d), 7.24-7.29 (2H, m), 7.38-7.42 (2H, m).

[0369] Intermediate (11)

[0370] (4-Fluorobenzyl)malononitrile

[0371] m.p.: 117.2° C.

[0372] Intermediate (12)

[0373] (3,4-Dichlorobenzyl)malononitrile

[0374] m.p.: 83.3° C.

[0375] Intermediate (13)

[0376] (2,4-Dichlorobenzyl)malononitrile

[0377] m.p.: 62.5° C.

[0378] Intermediate (14)

[0379] (4-(Trifluoromethylthio)benzyl)malononitrile

[0380]¹H-NMR (CDCl₃, TMS, 6 (ppm)): 3.15 (2H, d), 3.95 (1H, t), 7.37(2H, d), 7.70 (2H, d).

[0381] Intermediate (15)

[0382] (1-(4-Trifluoromethoxyphenyl))-2-propenylmalononitrile

[0383]¹H-NMR (CDCl₃, TMS, 6 (ppm)): 3.95-4.03 (2H, m), 5.40-5.53 (2H,m), 6.08-6.19 (1H, m), 7.28 (2H, d), 7.39 (2H, d).

[0384] Specific examples of the present compounds are shown in Table 1with the compound numbers. TABLE 1 The compounds of formula (Y): (Y)

No. R¹ R² m R³ (R⁵)_(n) R⁶ 1 H H 1 cyclopropyl — Cl 2 H H 1 cyclopropyl— OCF₃ 3 H H 1 cyclobutyl — OCF₃ 4 H H 1 cyclobutyl — SCF₃ 5 H H 12,2-dichlorocyclopropyl — OCF₃ 6 H H 1 cyclopropyl — CF₃ 7 H H 1cyclobutyl — CF₃ 8 H H 1 2,2-dichlorocyclopropyl — Cl 9 H H 12,2-dichlorocyclopropyl — CN 10 H H 1 2,2-dichlorocyclopropyl — CF₃ 11 HH 2 cycloplopyl — CF₃ 12 H H 2 cycloplopyl — Cl 13 H H 2 cycloplopyl3-Cl Cl 14 H H 2 cycloplopyl 3-F F 15 H H 2 cycloplopyl 3-F CF₃ 16 H H 2cycloplopyl — CN 17 H H 2 cycloplopyl — NO₂ 18 CH₃ H 2 cycloplopyl — Cl19 H H 2 cyclobutyll — CF₃ 20 H H 2 cyclobutyl 3-F CF₃ 21 H H 2cyclobutyl 3-Cl Cl 22 H H 2 cyclobutyl — CN 23 CH₃ H 2 cyclobutyl 3-F Cl24 CH(CH₃)₂ H 2 cyclobutyl — NO₂ 25 H H 1 2,2-difluorocyclopropyl — CN26 H H 1 2,2-difluorocyclopropyl — CF₃ 27 H H 1 2,2-difluorocyclopropyl3-F F 28 H H 1 2,2-difluorocyclopropyl — OCF₃ 29 H H 22,2-dichlorocyclopropyl — Cl 30 CH₃ H 2 2,2-dichlorocyclopropyl — CN 31H H 2 2,2-dichlorocyclopropyl — CF₃ 32 H H 2 2,2-difluorocyclopropyl3-CF₃ H 33 H H 2 2,2-difluorocyclopropyl — CF₃ 34 H H 22,2-difluorocyclopropyl 3-Cl CF₃ 35 CH₃ H 2 2,2-difluorocyclopropyl — Cl

[0385] The following will describe some formulation examples whereinparts represent parts by weight. The present compounds are designated bytheir compound numbers shown in Table 1.

FORMULATION EXAMPLE 1

[0386] Nine parts of each of the present compounds (1) to (25) isdissolved in 37.5 parts of xylene and 37.5 parts of dimethylformamide,and 10 parts of polyoxyethylene styryl phenyl ether and 6 parts ofcalcium dodecylbenzenesulfonate are added thereto, followed by wellstirring and mixing, to give an emulsifiable concentrate for eachcompound.

FORMULATION EXAMPLE 2

[0387] To 40 parts of each of the present compounds (1) to (25) is added5 parts of Sorpol® 5060 (Toho Chemical Industry Co., Ltd.), followed bywell mixing, and 32 parts of Carplex® #80 (synthetic hydrated siliconeoxide fine powder; Shionogi & Co., Ltd.) and 23 parts of 300 meshdiatomaceous earth are added, which is mixed with a mixer to give awettable powder for each compound.

FORMULATION EXAMPLE 3

[0388] To 3 parts of each of the present compounds (1) to (25) are added5 parts of synthetic hydrated silicon oxide fine powder, 5 parts ofsodium dodecylbenzenesulfonate, 30 parts of bentonite, and 57 parts ofclay, followed by well stirring and mixing, and an appropriate amount ofwater is added to this mixture, followed by further stirring,granulation with a granulator, and air drying, to give a granule foreach compound.

FORMULATION EXAMPLE 4

[0389] First, 4.5 parts of each of the present compounds (1) to (25), 1part of synthetic hydrated silicon oxide fine powder, 1 part of DoriresuB (Sankyo Co., Ltd.) as a flocculant, and 7 parts of clay are well mixedwith a mortar, followed by stirring and mixing with a mixer. To theresulting mixture is added 86.5 parts of cut clay, followed by wellstirring and mixing, to give a dust for each compound.

FORMULATION EXAMPLE 5

[0390] Ten parts of each of the present compounds (1) to (25), 35 partsof white carbon containing 50 parts of polyoxyethylene alkyl ethersulfate ammonium salt, and 55 parts of water are mixed and pulverized bythe wet grinding method to give a formulation for each compound.

FORMULATION EXAMPLE 6

[0391] First, 0.5 parts of each of the present compounds (1) to (25) isdissolved in 10 parts of dichloromethane, which is mixed with 89.5 partsof ISOPAR® M (isoparaffin; Exxon Chemical Co.) to give an oilformulation for each compound.

FORMULATION EXAMPLE 7

[0392] First, 0.1 parts of the present compounds (1) to (25) and 49.9parts of NEO-CHIOZOL (Chuo Kasei K.K.) are put into an aerosol can, towhich an aerosol valve is attached. Then, 25 parts of dimethyl ether and25 parts of LPG are filled in the aerosol can, followed by shaking and,attachment of an actuator, to give an oil-based aerosol.

FORMULATION EXAMPLE 8

[0393] First, 0.6 parts of each of the present compounds (1) to (25),0.01 parts of BHT, 5 parts of xylene, 3.39 parts of deodorized kerosine,and 1 part of an emulsifier (Atmos 300; Atmos Chemical Co.) are mixed tobecome a solution. Then, this solution and. 50 parts of distilled waterare filled in an aerosol can, to which a valve part is attached, and 40parts of a propellant (LPG) is filled under pressure through the valvein the aerosol can to give a water-based aerosol.

[0394] The following test example will demonstrate that the presentcompounds are useful as the active ingredients of pesticidecompositions. The present compounds are designated by their compoundnumbers shown in Table 1.

TEST EXAMPLE 1 Pesticidal Test against Nilaparvata Lugens

[0395] Each formulation of the compound 5, 6, 7 and 10 obtainedaccording to Formulation Example 5 was diluted with water so that theactive ingredient concentration came to 500 ppm to prepare a test liquidfor each compound. And formulation of the compound 4 obtained accordingto Formulation Example 5 was diluted with water so that the activeingredient concentration came to 200 ppm to prepare a test liquid foreach compound.

[0396] Fifty grams of molding Bonsoru 2 (available from SumitomoChemical Co., Ltd.) was put into a polyethylene cup, and 10 to 15 seedsof rice were planted in the polyethylene cup. Then rice plants weregrown until the second foliage leaves developed and then cut into thesame height of 5 cm. The test liquid for application prepared above wassprayed at the rate of 20 ml/cup onto these rice plants. After the testliquid sprayed onto the rice plants were dried, the polyethylene cupwith the rice plants was placed in a large polyethylene cup and 30first-instar larvae of Nilaparvata lugens (brown planthopper) were setfree in the large cup, which was then kept covered and left in agreenhouse at 25° C. On the 6th day after the release of Nilaparvatalugens larvae, the number of Nilaparvata lugens parasitic on the riceplants was examined.

[0397] As a result, in the treatment with each of the compoundsdescribed above, the number of parasitic pests on the 6th day after thetreatment was not greater than 3.

TEST EXAMPLE 2 Pesticidal Test against Nilaparvata lugens

[0398] Each formulation of the compound 3, 4, 5, 6, 7 and 10 obtainedaccording to Formulation Example 5 was diluted with water so that theactive ingredient concentration came to 45.5 ppm to prepare a testliquid for each compound.

[0399] Fifty grams of molding Bonsoru 2 (available from SumitomoChemical Co., Ltd.) was put into a polyethylene cup having five holes of5 mm, and 10 to 15 seeds of rice were planted in the polyethylene cup.Then rice plants were grown until the second foliage leaves developedand the polyethylene cup with the rice plants was placed in a large cupcontaining 55 ml of the test liquid, which had been prepared asdescribed above, was poured. The rice plants were left in a greenhouseat 25° C. for 6 days and then cut into the same height of 5 cm. Thirtyfirst-instar larvae of Nilaparvata lugens were set free in the largecup, which was then kept covered and left in a greenhouse at 25° C. Onthe 6th day after the release of Nilaparvata lugens larvae, the numberof Nilaparvata lugens (brown planthopper) parasitic on the rice plantswas examined.

[0400] As a result, in the treatment with each of the compoundsdescribed above, the number of parasitic pests on the 6th day after thetreatment was not greater than 3.

TEST EXAMPLE 3 Pesticidal Test against Nilaparvata lugens

[0401] Each formulation of the compound 1 and 2 obtained according toFormulation Example 1 was diluted with water so that the activeingredient concentration came to 500 ppm to prepare a test liquid foreach compound.

[0402] A bundle of 3 to 4 of cotyledons (height of 3 to 5 cm) of ricewas immersed in the test liquid, which had been prepared as describedabove, for 1 minute. After the test liquid treated the rice plants wasdried, a filter paper moistened with 1 ml of water was place on a bottomof polyethylene cup and then the bundle of cotyledons of rice was placedon it. Thirty first-instar larvae of Nilaparvata lugens (brownplanthopper) were set free in the polyethylene cup, which was then keptcovered and left in a greenhouse at 25° C. On the 6th day after therelease of Nilaparvata lugens larvae, the number of Nilaparvata lugensparasitic on the rice plants was examined.

[0403] As a result, in the treatment with each of the compoundsdescribed above, the number of parasitic pests on the 6th day after thetreatment was not greater than 3.

TEST EXAMPLE 4 Pesticidal Test against Diabrotica undecimpunctata

[0404] Each formulation of the compound 1 and 2 obtained according toFormulation Example 1 was diluted with water so that the activeingredient concentration came to 50 ppm to prepare a test liquid foreach compound.

[0405] On the bottom of a polyethylene cup of 5 cm in diameter wasplaced a filter paper, to which the test liquid had been prepared asdescribed above, was added dropwise in an amount of 1 ml. One germinatedseed of corn and 30 to 50 eggs of Diabrotica undecimpunctata (southerncorn rootworm) was placed on the filter paper in the polyethylene cup,which was then kept covered and left in a room at 25° C. On the 6th dayafter, the number of surviving larvae of Diabrotica undecimpunctata wasexamined.

[0406] As a result, in the treatment with each of the compoundsdescribed above, the number of surviving pests on the 6th day after was0.

TEST EXAMPLE 5 Pesticidal Test against Musca domestics

[0407] Each formulation of the compound 2, 3, 4, 5, 6, 7 and 10 obtainedaccording to Formulation Example 5 was diluted with water so that theactive ingredient concentration came to 500 ppm to prepare a test liquidfor each compound.

[0408] On the bottom of a polyethylene cup of 5.5 cm in diameter wasplaced a filter paper on the same size, to which the test liquid hadbeen prepared as described above, was added dropwise in an amount of 0.7ml, and 30 mg of sucrose as a bait was placed on it. Ten female adultsof Musca domestics (house fly) were set free in the polyethylene cup,which was then kept covered. After 24 hours, their survival was examinedto determine the mortality.

[0409] As a result, in the treatment with each of the compoundsdescribed above, it was exhibited the mortality of 100%.

TEST EXAMPLE 6 Pesticidal Test against Blattalla germanica

[0410] Each formulation of the compound 1, 2, 4, 6, 7 and 10 obtainedaccording to Formulation Example 5 was diluted with water so that theactive ingredient concentration came to 500 ppm to prepare a test liquidfor each compound.

[0411] On the bottom of a polyethylene cup of 5.5 cm in diameter wasplaced a filter paper on the same size, to which the test liquid hadbeen prepared as described above, was added dropwise in an amount of 0.7ml, and 30 mg of sucrose as a bait was placed on it. Two male adults ofBlattalla germanica (German cockroach) were set free in the polyethylenecup, which was then kept covered. After 6 days, their survival wasexamined to determine the mortality.

[0412] As a result, in the treatment with each of the compoundsdescribed above, it was exhibited the mortality of 100%.

TEST EXAMPLE 7 Pesticidal Test against Culex pipiens pallens

[0413] Each formulation of the compound 1, 2, 3, 4, 5, 6, 7, 9 and 10obtained according to Formulation Example 5 was diluted with water sothat the active ingredient concentration came to 500 ppm to prepare atest liquid for each compound.

[0414] In 100 ml of ion-exchanged water, the test liquid had beenprepared as described above, was added dropwise in an amount of 0.7 ml(the concentration of active ingredient was 3.5 ppm). Twentyfinal-instar larvae of Culex pipiens pallens (common mosquito) were setfree in the solution. After 1 days, their survival was examined todetermine the mortality.

[0415] As a result, in the treatment with each of the compoundsdescribed above, it was exhibited the mortality of 100%.

INDUSTRIAL APPLICABILITY

[0416] The present invention makes it possible to effectively controlpests such as insect pests, acarine pests, and nematode pests.

1. A malononitrile compound of formula (Y):

wherein R¹ and R² are the same or different and independently C₁-C₅(halo)alkyl, C₁-C₅ (halo)alkyloxy, C₂-C₅ (halo)alkenyl, C₂-C₅(halo)alkynyl, hydrogen, or cyano; R³ is C₃-C₆ (halo)cycloalkyl; m is aninteger of 1 to 3; R⁵ is halogen, cyano, nitro, C₁-C₄ (halo)alkyl, C₂-C₄(halo)alkenyl, C₂-C₄ (halo)alkynyl, C₁-C₃ (halo)alkyloxy, C₁-C₄(halo)alkylthio, C₁-C₄ (halo)alkylsulfinyl, C₁-C₄ (halo)alkylsulfonyl,C₁-C₄ (halo)alkylcarbonyl, C₁-C₄ (halo)alkyloxycarbonyl, C₁-C₄(halo)alkylcarbonyloxy, phenyloxy, or phenylthio, in which the phenyloxyand phenylthio groups may optionally be substituted with halogen orC₁-C₃ alkyl; n is an integer of 0 to 4; R⁶ is hydrogen, halogen, cyano,nitro, C₁-C₄ (halo)alkyl, C₂-C₄ (halo)alkenyl, C₂-C₄ (halo)alkynyl,C₁-C₄ (halo)alkyloxy, C₁-C₄ (halo)alkylthio, C₁-C₄ (halo)alkylsulfinyl,C₁-C₄ (halo)alkylsulfonyl, C₁-C₄ (halo)alkylcarbonyl, C₁-C₄(halo)alkyloxycarbonyl, C₁-C₄ (halo)alkylcarbonyloxy, phenyloxy, orphenylthio, in which the phenyloxyl and phenylthio groups may optionallybe substituted with halogen or C₁-C₃ alkyl; with the proviso that when nis 2 or more, then R⁵'s are the same or different from each other. 2.The malononitrile compound according to claim 1, wherein R⁶ is halogen,cyano, nitro, C₁-C₄ haloalkyl, C₁-C₄ haloalkyloxy or C₁-C₄haloalkylthio.
 3. The malononitrile compound according to claim 1,wherein R¹ and R² are both hydrogen.
 4. The malononitrile compoundaccording to claim 1, wherein R³ is cyclopropyl, cyclobutyl, or2,2-dichlorocyclopropyl, and m is
 1. 5. The malononitrile compoundaccording to claim 1, wherein R¹ and R² are the same or different andindependently C₁-C₃ (halo)alkyl, C₁-C₃ (halo)alkyloxy, C₂-C₄(halo)alkenyl, C₂-C₄ (halo)alkynyl, hydrogen, or cyano; R⁵ and R⁶ arethe same or different and independently halogen, cyano, nitro, C₁-C₃haloalkyl, C₁-C₃ haloalkyloxy, C₁-C₃ (halo)alkylthio, C₁-C₃(halo)alkylsulfinyl, C₁-C₃ (halo)alkylsulfonyl, C₁-C₃(halo)alkylcarbonyl, or C₁-C₃ haloalkyloxycarbonyl.
 6. The malononitrilecompound according to claim 5, wherein R³ is C₃-C₅ (halo)cycloalkyl andm is
 1. 7. A pesticide composition comprising the malononitrile compoundof claim 1 as an active ingredient and a carrier.
 8. A pest controllingmethod comprising applying a pesticidally effective amount of themalononitrile compound of claim 1 to pests or habitats of pests.
 9. Thepest controlling method according to claim 7, wherein the pests areinsect pests.
 10. Use of the malononitrile compound of claim 1 as anactive ingredient of a pesticide.